Effect of initiators and ethoxylation degree of non‐ionic emulsifiers on vinyl acetate and butyl acrylate emulsion copolymerization in the loop reactor

Vinyl acetate and butyl acrylate copolymers were synthesized in the presence of ammonium persulfate and potassium persulfate initiators, mixture of non‐ionic and anionic emulsifiers, and polyvinyl alcohol as protective colloid in a loop reactor. The monomer ratio was chosen 85:15. The series of non‐ionic emulsifiers, which have 10–40 moles ethoxylated nonyl phenol, were combined with Nansa 66 (sodium dodecyl benzene sulfonate). The effects of the initiators on the physicochemical properties of copolymers were investigated by measuring conversion, viscosity, molecular weight, molecular weight distribution, and surface tension, respectively by using gravimetric method, Brookfield viscometer, gel permeation chromatograpy (GPC), and ring method. The effects of ethoxylation degrees of the non‐ionic emulsifiers to the same properties of copolymers were also investigated. It was determined that the copolymer viscosities showed different tendency for two initiators. They were increased by the increasing ethoxylation degree of the non‐ionic emulsifier for ammonium persulfate. In contrast, latex viscosity was decreased by increasing the ethoxylation degree in presence of potassium persulfate. Similar changes were also found in number average molecular weights of copolymers. On the other hand, weight average molecular weights of copolymers increased by increasing the ethoxylation degree of the non‐ionic emulsifier for both initiators. In the case of potassium persulfate, the surface tension values of copolymers increased by increasing the ethoxylation degree, but generally increasing the ethoxylation degree did not affect the surface tension of copolymer very seriously for two initiators. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 537–543, 2003     

乙酸乙烯酯-丙烯酸异辛酯-乙烯基乙酰氧基硅烷的乳液聚合

制备了乙酸乙烯酯-丙烯酸异辛酯(2-EHA)-乙烯基乙酰氧基硅烷三元共聚胶乳,研究了聚合工艺、乳化剂、保护胶和2-EHA质量分数对共聚反应、胶乳性能及共聚物性能的影响。结果表明,该乳液聚合体系中,预乳化工艺明显优于半连续法工艺;当以十二烷基硫酸钠／聚乙二醇辛基苯基醚为复合乳化剂、以聚乙烯醇为保护胶时,聚合反应平稳,所得胶乳具有很好的稳定性;随着2-EHA质量分数的增加,胶乳稳定性逐渐提高,共聚物的玻璃化转变温度和胶乳的最低成膜温度降低,但2-EHA对前者的影响明显大于对后者的影响;乳胶膜的吸水量在200h后达到饱和。     

Off‐line monitoring of butyl acrylate and vinyl acetate homopolymerization and copolymerization in toluene

A study of butyl acrylate (BA) and vinyl acetate (VAc) solution homopolymerization and copolymerization in toluene was carried out. The conversion and copolymer composition were monitored using traditional techniques (gravimetry and ¹H‐NMR spectroscopy) and attenuated total reflectance‐Fourier transform IR (ATR‐FTIR) spectroscopy with a diamond‐composite probe and light conduit technology. The peak height of the characteristic absorbances of the monomer(s) during the course of the reaction was used to calculate the conversion and copolymer composition for the ATR‐FTIR monitoring. The data obtained using a ReactIR? 1000 reaction analysis system in the off‐line mode showed very good agreement with data obtained using traditional techniques. The solvent effects on BA and VAc solution homopolymerizations and copolymerizations in toluene were also investigated. Improvement to model predictions was obtained by allowing the lumped constant (k_p/k) to vary with the solvent concentration. Experimental data and model predictions of the number‐ and weight‐average molecular weights for the investigated systems are also presented. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2958–2977, 2001     

Semicontinuous heterophase copolymerization of vinyl acetate and butyl acrylate

Vinyl acetate (VAc) and butyl acrylate (BuA) were copolymerized in heterophase by a semicontinuous process (unseeded) and compared with the seeded semicontinuous microemulsion polymerization of the same monomers. A mixture of sodium dodecyl sulfate (SDS) and poly(ethylene oxide) dodecyl ether (Brij‐35®) were used as surfactants. The effects of monomer addition rate (R_a) and surfactants concentrations (4 or 1 wt % with respect to the initial mixture of reaction) on polymer and latex properties were studied. High copolymer content latexes (24–36 wt %) with average particle diameters (D_p) from 38 to 55 nm and relatively narrow particle size distributions, high polymerization rates, weight ratios of polymer to surfactant (P/S) from 13.3 to 32.8 were obtained. The number‐average molecular weights (M_n) were between 96,000 and 188,000 g/mol. Homogeneous copolymer compositions were obtained throughout the reaction for both, seeded and unseeded processes, which is not possible by the usual batch microemulsion process. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

氯乙烯-丙烯酸酯-醋酸乙烯酯三元共聚乳液的研究开发

采用乳液接枝共聚和核壳聚合相结合的工艺，用十二烷基硫酸钠作为新型种子乳化剂合成氯乙烯－丙烯酸酯－醋酸乙烯酯接枝共聚乳液，该乳液经Autosizeu IIC型激光粒径仪和DSC曲线测定具有核壳结构特征，用于纺织织物涂层，各项指标完全达到产品所规定的标准，效果很好。     

A systematic approach to the study of multicomponent polymerization kinetics: butyl acrylate/methyl methacrylate/vinyl acetate. III. Emulsion homopolymerization and copolymerization in a pilot plant reactor

A systematic study of the terpolymerization of butyl acrylate/methyl methacrylate/vinyl acetate (BA/MMA/VAc) is being conducted. In this third stage of the study,

1 Parts 1 and 2: Dubé, M. A. & Penlidis, A., Polymer, 36 (1995) 587. Dubé, M. A. & Penlidis, A., Macromol. Chem. Phys., 196 (1995) 1101.

emulsion homopolymerizations and copolymerizations of the monomers comprising the BA/MMA/VAc system were performed in a 5 litre stainless steel pilot plant reactor, mainly for troubleshooting purposes and as a precursor to the detailed terpolymerization experiments to follow. First, a search for a stable emulsion recipe was conducted. At the same time, experimental procedures were established for the 5 litre pilot plant reactor along with product characterization techniques. Finally, selective emulsion homopolymerizations and copolymerizations were run for each of the three monomers and each combination of the three monomers, respectively. The polymers produced were characterized for conversion, composition, molecular weight and particle size. Although the emphasis of the experiments was to establish recipes, techniques, and procedures for emulsions terpolymerization, several useful observations were made regarding the kinetics even from these troubleshooting experiments.     

丙烯酸乙酯与含环氧基烯类单体的乳液共聚合及共聚物表征

以乳液共聚合法合成了丙烯酸乙酯／含环氧基烯类单体共聚物,研究了含环氧基单体的种类,聚合工艺对单体转化率,共聚物相对分子质量和凝胶含量的影响,结果表明,以甲基丙烯酸缩水甘油酯作硫化点单体,单体的转化率和共聚物的相对分子质量较高;采用连滴加单体、“饥饿”态下聚合,有利于甲基丙烯酸缩水甘油酯在共聚物链上均匀分布;硫醇全部加入预聚单体中,共聚物的相对分子质量高;用ＩＲ＾１Ｈ－ＮＭＲ表征了共聚物结构和环氧基     

Emulsion copolymerization in a tubular reactor

A study was conducted on the emulsion copolymerization of vinyl acetate and butyl acrylate in a tubular reactor. It was performed at a constant temperature of 60°C and at different fluid velocities and feed compositions. Conversion, particle size distribution, and copolymer composition were measured, respectively, with gravimetric method, laser light scattering, and nuclear magnetic resonance. Maximum conversions were found for each of the monomer compositions; this maximum conversion varied, however, with the recipe used. The amount of butyl acrylate has a direct effect on the number of particles and on the final conversion. In lower levels of butyl acrylate particle size distribution is wide and bimodal. High levels of butyl acrylate leads to narrow and monomodal particle size distribution. Therefore the level of butyl acrylate and the velocity of fluid flowing inside the tube have strong effects on the shape (monomodal‐bimodal) and the width of particle size distributions. This effect may vary at different levels of butyl acrylate and flow rate. The results obtained from copolymer composition show that an alternating block copolymer is made during the reaction. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 833–842, 2000     

Semicontinuous emulsion polymerization of vinyl acetate: Effect of ethoxylation degree of nonionic emulsifiers

Poly(vinyl acetate) latices were prepared in the presence of an ammonium persulfate initiator, 10–50 mol of an ethoxylated nonylphenol nonionic emulsifier, and a poly(vinyl alcohol) colloid stabilizer by applying semicontinuous emulsion polymerization (delayed monomer and initiator addition process) in a laboratory scale similar to industrial practice. Two approaches were applied: the molar concentration of the nonionic emulsifier was kept constant and the weight ratios in the polymerization recipe varied or the weight ratios were kept constant. The effects of the change in the ethoxylation degree of the emulsifier to the final latex viscosity, average polymer molecular weight, polymer grafting degree, surface tension of the latex, and the surface free energy of the dried films were investigated. It was determined that the resultant latex viscosity decreases and the viscosity‐average polymer molecular weight increases with increase of the nonionic emulsifier ethoxylation degree. The increase of the ethoxylation degree does not seriously affect the surface tension of the resultant latex or the surface free energy of the dried poly(vinyl acetate) films. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 844–851, 2002     

有机硅氧烷改性醋酸乙烯酯-丙烯酸酯乳液的合成与性能

采用种子乳液聚合,引入乙烯基三甲氧基硅烷(A-171),以十二烷基苯磺酸钠(DSB)和壬基酚聚氧乙烯(20)醚(OP-10)作复合乳化剂,以过硫酸钾(KPS)为引发剂,在反应温度为78±2℃条件下,合成了A-171改性醋酸乙烯酯(VAc)-丙烯酸酯共聚乳液。实验采用单体滴加工艺,考察了配方中丙烯酸丁酯(BA)、甲基丙烯酸(MAA)和A-171用量对共聚物性能和乳液聚合过程的影响,并用红外光谱仪(FTIR)、粒度仪和差示量热扫描仪(DSC)对共聚物的结构及性能进行了表征。结果表明,引入w(BA)=10%~15%(相对于配方中单体总质量,下同)、w(MAA)=4%、w(A-171)=1%到VAc-丙烯酸酯共聚物乳液中,共聚物乳液涂膜的吸水率<5.0%,耐寒性通过10个循环,60℃加速贮存稳定性>100 d。     

淀粉接枝丙烯酸异辛酯-醋酸乙烯共聚反应的研究

采用乳液聚合的方法,以硝酸铈铵为引发剂,十二烷基硫酸钠为乳化剂,重点考察了淀粉与醋酸乙烯／丙烯酸异辛酯的接枝共聚反应中引发剂浓度、单体浓度、反应温度、反应时间等条件对接枝率、接枝效率以及接枝反应速率的影响,得到了较为理想的产物。结果表明,接枝率最高可达248.9％,接枝效率可达72.1％,单体转化率可达94.3％。     

Starve fed emulsion copolymerization of vinyl acetate and 1‐hexene at ambient pressure

A novel emulsion copolymer of vinyl acetate (VAc) and 1‐hexene was synthesized at ambient pressure. The feeding technique, initiation system and reaction time of the copolymerization were optimized based on molecular characteristics such as the weight contribution of 1‐hexene in the copolymer chains and glass transition temperature (T_g) as well as on bulk properties like minimum film‐formation temperature (MFFT) and solid content. According to nuclear magnetic resonance spectroscopy and differential scanning calorimetry results, the combination of starve feeding and redox initiation, within a reaction time of 4 h, effectively led to the copolymerization at ambient pressure between highly reactive polar VAc monomers and non‐polar 1‐hexene monomers of low reactivity. The copolymer showed a lower T_g and MFFT, and a reasonable solid content compared to the poly(vinyl acetate) (PVAc) homopolymer. The consumption rate, hydrolysis of acetate groups and chain transfer reactions during the polymerization were followed using infrared spectroscopy. Based on the results, the undesirable reactions between the VAc blocks were hindered by the neighbouring 1‐hexene molecules. Tensile testing revealed an improvement in the toughness and elongation at break of VAc–1‐hexene films compared to PVAc films. © 2014 Society of Chemical Industry     

醋酸乙烯酯/马来酸/丙烯酸丁酯无皂共聚乳液研究

采用无皂乳液聚合方法合成聚醋酸乙烯酯/马来酸/丙烯酸丁酯乳液。以透射电镜观察乳胶粒的表面形态并测量粒径,对乳胶粒的增长机理进行了分析。以转化率、吸水性、拉伸强度和乳液的稳定性为主要指标考查了共聚单体用量、pH等因素对乳液性能的影响。结果表明,马来酸占总单体量的3%,丙烯酸丁酯占8%,pH为6时共聚乳液具有良好的性能。     

The effectiveness of magnesium carbonate‐based flame retardants for poly(ethylene‐co‐vinyl acetate) and poly(ethylene‐co‐ethyl acrylate)

In this report we outline recent work on the evaluation of magnesium carbonate‐based flame retardants for polymers commonly used in halogen‐free flame retardant wire and cable applications: poly(ethylene‐co‐vinyl acetate) (EVA) and poly(ethylene‐co‐ethyl acrylate) (EEA). Natural magnesium carbonate (magnesite), synthetic magnesium carbonate (hydromagnesite), and hydromagnesite/huntite blends were combined with EVA or EEA and tested for flame retardancy effectiveness with the cone calorimeter. The flammability results showed that the effectiveness of these carbonates was polymer dependent, suggesting that polymer degradation chemistry played a role in the flammability reduction mechanism. Hydromagnesites were, in general, more effective in reducing flammability, being comparable in performance to magnesium hydroxide. Finally, we report some polymer–clay (organically treated montmorillonite and magadiite) + magnesium carbonate flame retardant results which showed that the nanocomposite yielded mixed results. Specifically, the polymer–clay nanocomposite samples did not always yield the greatest reductions in peak heat release rate. Copyright © 2007 John Wiley & Sons, Ltd.     

甲基丙烯酸甲酯-丙烯酸乙酯乳液共聚动力学研究

为了合成适于药物包衣用的甲基丙烯酸甲酯-丙烯酸乙酯(MMA-EA)共聚物胶乳,对以非离子型乳化剂OP-10为乳化剂、过硫酸钾为引发剂的MMA-EA乳液共聚动力学进行了研究。发现初期共聚速率随着乳化剂浓度、引发剂浓度和聚合温度的增加而增大,这是由于共聚物乳胶粒子平均粒径随着乳化剂、引发剂浓度和聚合温度的增加而减小,乳胶粒子数目增加所致。通过调节乳化剂、引发剂以及反应温度可以达到合适的聚合反应速率,最终合成出转化率大于95%的MMA-EA共聚乳液。     

醋酸乙烯酯与丙烯酸-2-羟基乙酯乳液共聚

研究了醋酸乙烯酯与丙烯酸-2-羟基乙酯共聚的合成路线，通过乳液聚合所制得的共聚产物可有效地改善聚醋酸乙烯酯的耐水性能与粘接性能；对影响共聚反应的各种因素进行了分析，并通过红外谱图和差热扫描量热分析法确定了共聚产物的生成。     

Prediction and experiment of core–shell particle morphology of vinyl acetate and butyl acrylate

In this article, the particle morphology in emulsion polymerization of the poly(vinyl acetate) (PVAc)/poly(butyl acrylate) (PBA) system is investigated. With the use of the basic data in literature, the relevant interface tensions and viscosity are estimated with the equation proposed in literature. The time achieved to equilibrium morphology is predicted with cluster dynamics proposed by Gonzalez. The experiment result is consistent with that of prediction. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2930–2937, 2002; DOI 10.1002/app.10297     

Free radical copolymerization behavior of vinyl acetate with butyl acrylate in the presence of GeCl4 and BCl3

No alternating copolymers of vinyl acetate (VAc) and butyl acrylate (BA) were obtained by free radical copolymerization in the presence of GeCl₄ and BCl₃ (compared with the acrylic acid–vinyl acetate copolymerization system). By ultraviolet spectral analysis, it was concluded that both BCl₃ and GeCl₄ can form complexes with butyl acrylate. The BA–BCl₃ complex constants were determined by ¹H NMR; K_B=33·2 (25°C). The reason for the gel formation in the BA–Vac–BCl₃ copolymerization system was discussed. When vinyl acetate reacted with BCl₃, cationic polymerization probably occurred. A white gel product probably resulted from the polymerization of the BA–BCl₃ complex. © 1998 SCI.     

木薯淀粉/VAc-MA接枝共聚物的合成研究

通过正交试验设计,研究醋酸乙烯酯和丙烯酸甲酯两种单体接枝改性木薯淀粉的影响因素。利用SAS统计分析得出适宜的工艺条件:引发剂浓度16mmol.L-1,总单体浓度1.45mol.L-1,两单体配比(VAc/MA)为30/70,反应温度65℃,反应时间5h。采用红外光谱对该接枝共聚物结构进行了分析。     

On‐line monitoring of methyl methacrylate–vinyl acetate emulsion copolymerization

An adaptive calorimetric method, coupled with state estimators for emulsion copolymerization, is shown to provide accurate, on‐line information on the evolution of the composition and kinetics of an emulsion copolymerization. This method was evaluated for the emulsion copolymerization of methyl methacrylate–vinyl acetate (MMA–VAc) under nonisothermal conditions. In addition to providing on‐line estimates of the number of moles of each polymerizing species in the reactor, the state estimator provides a value for a lumped kinetic parameter proportional to the product of n N_p. This information can be combined with off‐line measurements to study the evolution of polymerization kinetics and to explain the trends observed for the molecular weight distribution and glass transition temperatures. Values of n were found to vary from 0.5 to 30 for the homopolymerization of MMA. However, the presence of VAc in the copolymerizing system drastically reduces n . This can lead to a dramatic increase in the average molecular weight of the copolymer since it alters the ratio of propagation to termination in the polymerizing particles. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1667–1683, 2000